CN108191438A - A kind of phosphorous nitride combined silicon carbide material and preparation method thereof - Google Patents
A kind of phosphorous nitride combined silicon carbide material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to technical field of fire-resistant material preparation, relate generally to a kind of phosphorous high antioxidant nitride combined silicon carbide material and preparation method thereof.A kind of raw material of the phosphorous nitride combined silicon carbide material proposed forms and mass percent is：Metallic silicon power 3 ~ 25%, silicon-carbide particle 60 ~ 70%, carbide fine powder 8 ~ 30%, silicon powder 0 ~ 6%, phosphorus additive 0.1 ~ 3%；The phosphorous nitride combined silicon carbide material, using silicon carbide as principal crystalline phase, silicon nitride is generated by the nitridation reaction of metallic silicon and nitrogen, and metallic silicon, silicon powder and nitrogen nitridation reaction generation silicon oxynitride, so as to formed using silicon nitride or silicon oxynitride with silicon nitride as the phosphorous nitride combined silicon carbide material with reference to phase.Substantially weightening and volume expansion caused by the phosphorous nitride combined silicon carbide material of the present invention can resist oxidation, prevents thus caused material damage, extends service life.
Description
Technical field
The invention belongs to technical field of fire-resistant material preparation, relate generally to a kind of phosphorous nitride combined silicon carbide material and
Preparation method.
Background technology
Silicon carbide because its with high intensity, hardness and excellent anti-oxidant, corrosion and it is wear-resisting when performances due to be widely used
In abrasive material and resistance to material field.Nitride（Silicon nitride, silicon oxynitride or silicon nitride and silicon oxynitride complex phase）Silicon carbide fire resisting
Material is with thermal conductivity is big, linear expansion coefficient is small, room temperature and elevated temperature strength height, good thermal shock, resistant to chemical etching and high temperature are resistance to
Mill property is excellent to wait excellent properties, extensively should have in fields such as steel, nonferrous metallurgy, chemistry, electric power, ceramics and waste incinerators
With.
One of the main reason for continued oxidation under high temperature is the damage of nitride combined silicon carbide material.In air atmosphere
In, carbofrax material, which is heated to certain temperature, will occur passive oxidation, and starting the temperature of oxidation and the granularity of material has
It closes, granularity is more than the silicon-carbide particle of 0.1mm, starts oxidizing temperature at 800 DEG C or so, granularity is less than the silicon carbide of 0.1mm
It starts oxidizing temperature and wants more relatively low micro mist, specifically related with the size of granularity and ratio.900 ~ 1300 DEG C of Oxidation of SiC
Though speed is slow, surface is generally hardly formed SiO2Protective film, at 1300 DEG C or more, Oxidation of SiC rear surface generally can shape
Into SiO2Protective film.In the presence of having vapor, the oxidation of silicon carbide can be significantly accelerated, so as to exacerbate the damage of carbofrax material
It ruins.In nitride combined silicon carbide material, nitride be production during nitridation generation combination phase, mostly in crystal whisker-shaped,
Column or sheet, for oikocryst phase silicon carbide, specific surface area bigger, reactivity higher, so in identical gas
Under the conditions of atmosphere, the beginning oxidizing temperature of nitride can be lower, and oxidation rate also faster can reduce material with reference to the transformation of phase
Bond strength, and oxidation product SiO2Crystal transfer can occur in the heating and cooling process of each interval blowing out, and with larger
Bulk effect, so as to generate larger stress cause material internal generate micro-crack, cause the strength of materials attenuation even crack
Damage, affects carbofrax material in the service life on certain industrial equipments, such as is in the process of running vapor, sky
The Experiment Coke Oven side wall liner of gas, coke-stove gas mixed atmosphere.
Over the past decade, coking industry is fast-developing by the growth that steel produces and consumes, with the expansion of coke production capacity
Exhibition, has been further exacerbated by the imbalance between supply and demand of coking coal resource, though China is Coal Energy Source big country, coking coal resource total amount is richer
Richness, but Category disposition is clearly present imbalance, and its main feature is that high-quality caking coal shortage of resources, the poor coking coal of coking capacity is opposite
It is abundant.Coke making and coal blending can not only optimize coking coal resource configuration, but also can guarantee the quality of coke, therefore Coal Blending Technology obtains extensively
Application.Experiment Coke Oven is the small coke oven of the industrial coke oven working environment of simulation, is the common experimental facilities of coke making and coal blending, and design is closed
The Experiment Coke Oven of reason and the coke oven of actual industrial production have good relevance, and experimental result can preferably instruct practical life
Production, so, Experiment Coke Oven is the standard configuration of almost all of coke-oven plant and related research institutes.
Currently, most Experiment Coke Oven coking chamber wall is using entirety Sialon-SiC brick masonries, because of the carbofrax material
Anti-rapid heat cycle performance is good, and thermal conductivity factor is high, saves the energy, and can realize the real both sides heating to coal charge.Carbonization chamber furnace body
It is it has to be ensured that tight leak-free, so the silicon carbide brick built by laying bricks or stones uses the form of " snap fastener " substantially, but this form
Shortcoming is substantially without adjustable expansion space between brick and brick, is expanded once being generated inside brick body in use, stove
Wall will very likely crack.During practical pilot production, just often there is cooking camber furnace wall swelling cracking
Phenomenon causes the oven wall of coke oven carbonization chamber service life that Sialon-SiC bricks are integrally built by laying bricks or stones undesirable.The main reason is that in cooking camber
Oxidation of the oxidizing atmosphere to Sialon-SiC materials.
Process of coking substantially undergoes following three stage：1）Dry degassing, 2）Coal coheres to form semicoke generation coal gas, and 3）Polycondensation
Reaction, is precipitated a large amount of coal gas, semicoke becomes coke.The running temperature of cooking camber due to blending ratio and makes at 700 DEG C ~ 1050 DEG C
With the difference of coal, the water content of mixed coal is in 15%-30% or so, in the dry degassing stage, moisture evaporation in mixed coal and
The indoor air of coking forms oxidizing atmosphere, when coking indoor temperature is up to 800 DEG C or more, starts to aoxidize Sialon-SiC materials
Material, oxidation product SiO2It is aoxidized with Sialon and Al is precipitated2O3Sustained response, which forms mullite, causes material volume constantly to expand, not
The oxidation product SiO of reaction2Crystal transfer can occur in the heating and cooling process of each interval blowing out, and with larger volume
Effect will cause furnace wall cracking damage after the volume expansion of each piece of brick is saved bit by bit to a certain extent.
Therefore, to solve the problems, such as Experiment Coke Oven cooking camber furnace wall short life, used furnace wall material must have compared with
Good volume stability, i.e., in by air and the oxidation of vapor mixed gas and interval blowing out heating and cooling process, the body of material
Product variation is little.
Invention content
In order to solve the above technical problems, the purpose of the present invention is a kind of phosphorous nitride combined silicon carbide material and its preparations
Method.
The present invention uses the following two kinds technical solution to complete above-mentioned purpose：
A kind of phosphorous nitride combined silicon carbide material, the raw material composition and quality of the phosphorous nitride combined silicon carbide material
Percentage is：Metallic silicon power 3 ~ 25%, silicon-carbide particle 60 ~ 70%, carbide fine powder 8 ~ 30%, silicon powder 0 ~ 6%, phosphorus additive
0.1~3%；The phosphorous nitride combined silicon carbide material, using silicon carbide as principal crystalline phase, passes through the nitridation of metallic silicon and nitrogen
The nitridation reaction generation silicon oxynitride of reaction generation silicon nitride and metallic silicon, silicon powder and nitrogen, so as to be formed with silicon nitride
Or silicon oxynitride and silicon nitride are the nitride combined silicon carbide material with reference to phase.
The phosphorus additive is solid-state or liquid.
The phosphorus additive is solid-state, as sodium tripolyphosphate, calcium phosphate, magnesium phosphate, basic zirconium phosphate, chromium phosphate, di(2-ethylhexyl)phosphate
The mixing of one or more of hydrogen aluminium, composite phosphate.
The phosphorus additive is liquid, and the phosphorus additive is molten for the phosphoric acid of phosphate solution or concentration 20%-85%
Liquid.
The phosphate solution is one in sodium tripolyphosphate solution, sodium hexametaphosphate solution, phosphate dihydrogen aluminum solution
Kind or several mixing.
The addition of the phosphorus additive is 0.3 ~ 1.5%.
The preparation method for preparing above-mentioned phosphorous nitride combined silicon carbide material is：
Solid-state phosphorus additive is mixed with metallic silicon power, silicon-carbide particle, carbide fine powder and silicon powder, through being kneaded, being molded,
Dry, Nitride firing, forms phosphorous nitride combined silicon carbide material；It is as follows：
（1）Carbide fine powder, metallic silicon power, silicon powder and phosphorus additive are blended together into mixing fine powders in advance, then by mixing fine powders and carbon
Silicon carbide particle and the bonding agent mixing in kneading machine, on forming machine compression moulding green compact are made；
（2）By step（1）In the green compact that are pressed into be positioned over 60~180 DEG C and dried stage by stage, total drying time is no less than
24 hours；
（3）Above-mentioned dried green body is placed in high temperature firing under nitrogen atmosphere, heating up process is continuous warming process, most
High firing temperature is 1350~1500 DEG C, and soaking time is 5~15 hours；
（4）Cool to room temperature with the furnace, products obtained therefrom is the phosphorous nitrogen oxide combined silicon carbide material；
Or, the preparation method is：
（1）Carbide fine powder, metallic silicon power, silicon powder are blended together into mixing fine powders in advance, then by mixing fine powders and silicon-carbide particle and
Bonding agent mixing in kneading machine, on forming machine compression moulding green compact are made；
（2）By step（1）In the green compact that are pressed into be positioned over 60~180 DEG C and dried stage by stage, total drying time is no less than
24 hours；
（3）Above-mentioned dried green body is placed in high temperature firing under nitrogen atmosphere, heating up process is continuous warming process, most
High firing temperature is 1350~1500 DEG C, and soaking time is 5~15 hours；
（4）It cools to room temperature with the furnace and obtains nitride combined silicon carbide material；
（5）Obtained nitride combined silicon carbide material is put into the phosphorus additive of liquid, negative pressure impregnation 3-12 hours；
（6）, by after dipping nitride combined silicon carbide material carry out secondary heat treatment, heating up process be continuous warming mistake
Journey, 900 ~ 1100 DEG C of secondary heat treatment maximum temperature, soaking time 6-8 hours.
A kind of phosphorous nitride combined silicon carbide material proposed by the present invention, by adding at least one in the production process
Phosphorus additive introduces phosphoric acid or phosphate by way of negative pressure impregnation infiltration, and P elements or phosphate in raw material with adding
The silicon powder entered（SiO2）Or the SiO of oxidation process generation2And other trace impurities formation low-melting-point glass that raw material introduces mutually wraps
It wraps up in silicon-carbide particle and stromal surface or covering stomata inner wall, block stomata, barrier oxidation medium（Oxygen and water vapour）To material
The intrusion of material delays being aoxidized for material；Meanwhile P elements are glass network former, the presence of P elements can make eutectic glass
Glass is mutually more stable, can avoid or delay SiO in glass phase2Crystallization and crystal transfer caused by material volume expansion, so as to
Assign the better volume stability of material.
Using the antioxygenic property of standard ASTM-C863 test materials, the specific steps are：Each material respectively cuts 3 rulers
It is very little be 165 × 114 × 22mm sample, measure each sample mass and volume, be then placed in furnace muffle, be heated to 1000
DEG C, according to burner hearth size with 32kg/ (m3.h rate) is passed through water vapour, takes out sample measurement quality and volume within every 100 hours,
Total soaking time 500 hours.Its inoxidizability is weighed with quality of materials and volume change.
Table 1 lists the anti-saturation steam oxidation performance of various nitride combined silicon carbide products, and contains with the present invention
Phosphorous nitride object combined silicon carbide product compares.As can be seen that the phosphorous multiphase nitride combined silicon carbide product of product of the present invention
Volume expansion only has 0.3 ~ 1.0%, has good anti-oxidant volume stability.
1. various nitride combined silicon carbide product anti-saturation steam oxidation performances of table compare
Specific embodiment
Invention is illustrated with reference to following specific embodiments：
Comparative example 1：Silicon nitride combined silicon carbide（It is additive-free）
It is formulated according to mass percent design table 2
2 raw material proportioning of table
Various raw materials have been weighed according to aforementioned proportion, carbide fine powder, silica flour have been premixed 30 minutes in vibromill, mixing is made
Fine powder.Bonding agent is added in after silicon-carbide particle material is mixed 8 minutes in kneading machine during batch mixing, is mixed 5 minutes, water is then added in and mixes again
5 minutes, mixing fine powders are eventually adding, then 15 minutes mixed.
The material mixed is suppressed into molding machine the green body of 230 × 114 × 65mm, by green body as 120 DEG C
At a temperature of dry 24 hours.
Dried green body is placed in atmosphere furnace, is passed through nitrogen, be warming up to 1450 DEG C and keeps the temperature 15 hours.
Cut from the product after firing 3 sizes be 165 × 114 × 22mm sample, test 3 samples volume and
Quality is then placed in trial furnace.1000 DEG C are warming up to according to ASTM-C863 standards, with 32kg/ (m3.h rate) is passed through water steaming
Vapour keeps the temperature 500 hours.After blowing out cooling, volume and quality after its oxidation of taking-up sample testing calculate volume change and matter
Quantitative change rate.Test result：Volume change is respectively+3.35% ,+3.42% ,+3.28%, mass change for+3.14% ,+
3.26%、3.33%。
Comparative example 2：Multiphase nitride combined silicon carbide（It is additive-free）
It is formulated according to mass percent design table 3
3 raw material proportioning of table
Various raw materials have been weighed according to aforementioned proportion, carbide fine powder, silica flour, silicon powder have been premixed 30 minutes in vibromill,
Mixing fine powders are made；Bonding agent is added in after silicon-carbide particle material is mixed 8 minutes in kneading machine during batch mixing, is mixed 5 minutes, Ran Houjia
Enter water to mix 5 minutes again, be eventually adding mixing fine powders, then 15 minutes mixed；The material mixed is suppressed into 230 in molding machine
The green body of × 114 × 65mm, by green body as 24 hours dry at a temperature of 120 DEG C；Dried green body is placed in atmosphere furnace
In, nitrogen is passed through, 1450 DEG C is warming up to and keeps the temperature 15 hours.
Cut from the product after firing 3 sizes be 165 × 114 × 22mm sample, test 3 samples volume and
Quality is then placed in trial furnace.1000 DEG C are warming up to according to ASTM-C863 standards, with 32kg/ (m3.h rate) is passed through water steaming
Vapour keeps the temperature 500 hours.After blowing out cooling, volume and quality after its oxidation of taking-up sample testing calculate volume change and matter
Quantitative change rate.Test result：Volume change is respectively+2.83% ,+2.75% ,+2.77%, mass change for+2.95% ,+
3.02%、2.98%。
Comparative example 3：Sialon silicon carbide（It is additive-free）
It is formulated according to mass percent design table 4
4 raw material proportioning of table
Various raw materials are weighed according to aforementioned proportion, by carbide fine powder, silica flour, Al2O3Micro mist premixes 30 points in vibromill
Mixing fine powders are made in clock；Bonding agent is added in after silicon-carbide particle material is mixed 8 minutes in kneading machine during batch mixing, it is 5 minutes mixed, so
Water is added in afterwards to mix 5 minutes again, is eventually adding mixing fine powders, then 15 minutes mixed；The material mixed is pressed into molding machine
For the green body of 230 × 114 × 65mm, green body is dried 24 hours as at a temperature of 120 DEG C；Dried green body is placed in gas
In atmosphere stove, nitrogen is passed through, be warming up to 1450 DEG C and keeps the temperature 18 hours.
Cut from the product after firing 3 sizes be 165 × 114 × 22mm sample, test 3 samples volume and
Quality is then placed in trial furnace.1000 DEG C are warming up to according to ASTM-C863 standards, with 32kg/ (m3.h rate) is passed through water steaming
Vapour keeps the temperature 500 hours.After blowing out cooling, volume and quality after its oxidation of taking-up sample testing calculate volume change and matter
Quantitative change rate.Test result：Volume change is respectively+3.86% ,+3.75% ,+4.07%, mass change for+3.45% ,+
3.62%、4.18%。
Embodiment 1：It is formulated according to mass percent design table 5
5 raw material proportioning of table
Various raw materials are weighed according to aforementioned proportion, by carbide fine powder, silica flour, silicon powder, sodium tripolyphosphate in vibromill
Premix 30 minutes, is made mixing fine powders.Bonding agent is added in after silicon-carbide particle material is mixed 8 minutes in kneading machine during batch mixing, mixes 5
Minute, it then adds in water and mixes 5 minutes again, be eventually adding mixing fine powders, then 15 minutes mixed.
The material mixed is suppressed into molding machine the green body of 230 × 114 × 65mm, by green body as 120 DEG C
At a temperature of dry 24 hours.
Dried green body is placed in atmosphere furnace, is passed through nitrogen, be warming up to 1450 DEG C and keeps the temperature 15 hours.
Cut from the product after firing 3 sizes be 165 × 114 × 22mm sample, test 3 samples volume and
Quality is then placed in trial furnace.1000 DEG C are warming up to according to ASTM-C863 standards, with 32kg/ (m3.h rate) is passed through water steaming
Vapour keeps the temperature 500 hours.After blowing out cooling, volume and quality after its oxidation of taking-up sample testing calculate volume change and matter
Quantitative change rate.As a result it is：Volume change is respectively+0.55% ,+0.47% ,+0.63%, mass change for+1.35% ,+
1.30%、1.98%。
Embodiment 2：It is formulated according to mass percent design table 6
6 raw material proportioning of table
Various raw materials are weighed according to aforementioned proportion, by carbide fine powder, silica flour, silicon powder, sodium tripolyphosphate in vibromill
Premix 30 minutes, is made mixing fine powders.Bonding agent is added in after silicon-carbide particle material is mixed 8 minutes in kneading machine during batch mixing, mixes 5
Minute, it then adds in water and mixes 5 minutes again, be eventually adding mixing fine powders, then 15 minutes mixed.
The material mixed is suppressed into molding machine the green body of 230 × 114 × 65mm, by green body as 120 DEG C
At a temperature of dry 24 hours.
Dried green body is placed in atmosphere furnace, is passed through nitrogen, be warming up to 1450 DEG C and keeps the temperature 15 hours.
Cut from the product after firing 3 sizes be 165 × 114 × 22mm sample, test 3 samples volume and
Quality is then placed in trial furnace.1000 DEG C are warming up to according to ASTM-C863 standards, with 32kg/ (m3.h rate) is passed through water steaming
Vapour keeps the temperature 500 hours.After blowing out cooling, volume and quality after its oxidation of taking-up sample testing calculate volume change and matter
Quantitative change rate.As a result it is：Volume change is respectively+0.92% ,+0.87% ,+0.83%, mass change for+1.98% ,+
1.77%、+1.71%。
Embodiment 3：It is formulated according to mass percent design table 7
7 raw material proportioning of table
Various raw materials have been weighed according to aforementioned proportion, carbide fine powder, silica flour, calcium phosphate have been premixed 30 minutes in vibromill,
Mixing fine powders are made.Bonding agent is added in after silicon-carbide particle material is mixed 8 minutes in kneading machine during batch mixing, is mixed 5 minutes, Ran Houjia
Enter water to mix 5 minutes again, be eventually adding mixing fine powders, then 15 minutes mixed.
The material mixed is suppressed into molding machine the green body of 230 × 114 × 65mm, by green body as 120 DEG C
At a temperature of dry 24 hours.
Dried green body is placed in atmosphere furnace, is passed through nitrogen, be warming up to 1450 DEG C and keeps the temperature 15 hours.
Cut from the product after firing 3 sizes be 165 × 114 × 22mm sample, test 3 samples volume and
Quality is then placed in trial furnace.1000 DEG C are warming up to according to ASTM-C863 standards, with 32kg/ (m3.h rate) is passed through water steaming
Vapour keeps the temperature 500 hours.After blowing out cooling, volume and quality after its oxidation of taking-up sample testing calculate volume change and matter
Quantitative change rate.As a result it is：Volume change is respectively+0.74% ,+0.99% ,+0.87%, mass change for+1.75% ,+
2.32%、+2.03%。
Embodiment 4：It is formulated according to mass percent design table 8
8 raw material proportioning of table
Various raw materials have been weighed according to aforementioned proportion, carbide fine powder, silica flour, calcium phosphate have been premixed 30 minutes in vibromill,
Mixing fine powders are made.Bonding agent is added in after silicon-carbide particle material is mixed 8 minutes in kneading machine during batch mixing, is mixed 5 minutes, Ran Houjia
Enter water to mix 5 minutes again, be eventually adding mixing fine powders, then 15 minutes mixed.
The material mixed is suppressed into molding machine the green body of 230 × 114 × 65mm, by green body as 120 DEG C
At a temperature of dry 24 hours.
Dried green body is placed in atmosphere furnace, is passed through nitrogen, be warming up to 1450 DEG C and keeps the temperature 15 hours.
Cut from the product after firing 3 sizes be 165 × 114 × 22mm sample, test 3 samples volume and
Quality is then placed in trial furnace.1000 DEG C are warming up to according to ASTM-C863 standards, with 32kg/ (m3.h rate) is passed through water steaming
Vapour keeps the temperature 500 hours.After blowing out cooling, volume and quality after its oxidation of taking-up sample testing calculate volume change and matter
Quantitative change rate.As a result it is：Volume change is respectively+0.93% ,+1.0% ,+0.89%, mass change for+1.82% ,+
2.06%、+1.90%。
Embodiment 5：It is formulated according to mass percent design table 9
9 raw material proportioning of table
Various raw materials are weighed according to aforementioned proportion, by carbide fine powder, silica flour, silicon powder, sodium tripolyphosphate+calcium phosphate（Matter
Measure ratio 1：1）It is premixed 30 minutes in vibromill, mixing fine powders is made.Silicon-carbide particle material is mixed 8 points in kneading machine during batch mixing
Bonding agent is added in after clock, is mixed 5 minutes, water is then added in and mixes 5 minutes again, be eventually adding mixing fine powders, then 15 minutes mixed.
The material mixed is suppressed into molding machine the green body of 230 × 114 × 65mm, by green body as 120 DEG C
At a temperature of dry 24 hours.
Dried green body is placed in atmosphere furnace, is passed through nitrogen, be warming up to 1450 DEG C and keeps the temperature 15 hours.
Cut from the product after firing 3 sizes be 165 × 114 × 22mm sample, test 3 samples volume and
Quality is then placed in trial furnace.1000 DEG C are warming up to according to ASTM-C863 standards, with 32kg/ (m3.h rate) is passed through water steaming
Vapour keeps the temperature 500 hours.After blowing out cooling, volume and quality after its oxidation of taking-up sample testing calculate volume change and matter
Quantitative change rate.As a result it is：Volume change is respectively+0.71% ,+0.55% ,+0.68%, mass change for+1.53% ,+
1.45%、+1.87%。
Embodiment 6：It is formulated according to mass percent design table 10
10 raw material proportioning of table
Various raw materials are weighed according to aforementioned proportion, by carbide fine powder, silica flour, silicon powder, sodium tripolyphosphate+calcium phosphate（Matter
Measure ratio 1：1）It is premixed 30 minutes in vibromill, mixing fine powders is made.Silicon-carbide particle material is mixed 8 points in kneading machine during batch mixing
Bonding agent is added in after clock, is mixed 5 minutes, water is then added in and mixes 5 minutes again, be eventually adding mixing fine powders, then 15 minutes mixed.
The material mixed is suppressed into molding machine the green body of 230 × 114 × 65mm, by green body as 120 DEG C
At a temperature of dry 24 hours.
Dried green body is placed in atmosphere furnace, is passed through nitrogen, be warming up to 1450 DEG C and keeps the temperature 15 hours.
Cut from the product after firing 3 sizes be 165 × 114 × 22mm sample, test 3 samples volume and
Quality is then placed in trial furnace.1000 DEG C are warming up to according to ASTM-C863 standards, with 32kg/ (m3.h rate) is passed through water steaming
Vapour keeps the temperature 500 hours.After blowing out cooling, volume and quality after its oxidation of taking-up sample testing calculate volume change and matter
Quantitative change rate.As a result it is：Volume change is respectively+0.78% ,+0.95% ,+0.86%, mass change for+1.73% ,+
2.15%、+1.82%。
Embodiment 7：It is formulated according to mass percent design table 11
11 raw material proportioning of table
Various raw materials have been weighed according to aforementioned proportion, carbide fine powder, silica flour, silicon powder have been premixed 30 minutes in vibromill,
Mixing fine powders are made.Bonding agent is added in after silicon-carbide particle material is mixed 8 minutes in kneading machine during batch mixing, is mixed 5 minutes, Ran Houjia
Enter water to mix 5 minutes again, be eventually adding mixing fine powders, then 15 minutes mixed.
The material mixed is suppressed into molding machine the green body of 230 × 114 × 65mm, by green body as 120 DEG C
At a temperature of dry 24 hours.
Dried green body is placed in atmosphere furnace, is passed through nitrogen, be warming up to 1450 DEG C and keep the temperature 15 hours, after firing with
Stove is cooled to room temperature, and obtains multiphase nitride combined silicon carbide product.
Burned multiphase nitride combined silicon carbide product is positioned in a concentration of 50% phosphoric acid solution, sealing is taken out negative
- 0.05MPa is depressed into, is impregnated 6 hours.
The multiphase nitride combined silicon carbide product impregnated is positioned in kiln, is warming up to 900 DEG C, keeps the temperature 6 hours.
Cut from the product after firing 3 sizes be 165 × 114 × 22mm sample, test 3 samples volume and
Quality is then placed in trial furnace.1000 DEG C are warming up to according to ASTM-C863 standards, with 32kg/ (m3.h rate) is passed through water steaming
Vapour keeps the temperature 500 hours.After blowing out cooling, volume and quality after its oxidation of taking-up sample testing calculate volume change and matter
Quantitative change rate.As a result it is：Change rate is respectively+0.67% ,+0.95% ,+0.76%, mass change is+1.37% ,+2.18% ,+
1.84%。
Embodiment 8：It is formulated according to mass percent design table 12
12 raw material proportioning of table
Various raw materials have been weighed according to aforementioned proportion, carbide fine powder, silica flour, silicon powder have been premixed 30 minutes in vibromill,
Mixing fine powders are made.Bonding agent is added in after silicon-carbide particle material is mixed 8 minutes in kneading machine during batch mixing, is mixed 5 minutes, Ran Houjia
Enter water to mix 5 minutes again, be eventually adding mixing fine powders, then 15 minutes mixed.
The material mixed is suppressed into molding machine the green body of 230 × 114 × 65mm, by green body as 120 DEG C
At a temperature of dry 24 hours.
Dried green body is placed in atmosphere furnace, is passed through nitrogen, be warming up to 1380 DEG C and keep the temperature 15 hours, after firing with
Stove is cooled to room temperature, and obtains multiphase nitride combined silicon carbide product.
Burned multiphase nitride combined silicon carbide product is positioned in a concentration of 50% sodium tripolyphosphate solution, it is close
Envelope takes out negative pressure to -0.1MPa, impregnates 3 hours.
The multiphase nitride combined silicon carbide product impregnated is positioned in kiln, is warming up to 900 DEG C, keeps the temperature 6 hours.
Cut from the product after firing 3 sizes be 165 × 114 × 22mm sample, test 3 samples volume and
Quality is then placed in trial furnace.1000 DEG C are warming up to according to ASTM-C863 standards, with 32kg/ (m3.h rate) is passed through water steaming
Vapour keeps the temperature 500 hours.After blowing out cooling, volume and quality after its oxidation of taking-up sample testing calculate volume change and matter
Quantitative change rate.As a result it is：Volume change is respectively+0.64% ,+0.79% ,+0.71%, mass change for+1.50% ,+
2.02%、+1.78%。
Embodiment 9：It is formulated according to mass percent design table 13
13 raw material proportioning of table
Various raw materials have been weighed according to aforementioned proportion, carbide fine powder, silica flour, silicon powder have been premixed 30 minutes in vibromill,
Mixing fine powders are made.Bonding agent is added in after silicon-carbide particle material is mixed 8 minutes in kneading machine during batch mixing, is mixed 5 minutes, Ran Houjia
Enter water to mix 5 minutes again, be eventually adding mixing fine powders, then 15 minutes mixed.
The material mixed is suppressed into molding machine the green body of 230 × 114 × 65mm, by green body as 120 DEG C
At a temperature of dry 24 hours.
Dried green body is placed in atmosphere furnace, is passed through nitrogen, be warming up to 1400 DEG C and keep the temperature 15 hours, after firing with
Stove is cooled to room temperature, and obtains multiphase nitride combined silicon carbide product.
Burned multiphase nitride combined silicon carbide product is positioned over to a concentration of 50% sodium tripolyphosphate and hexa metaphosphoric acid
In sodium mixed solution（The concentration ratio of sodium tripolyphosphate and calgon is 1:1）, seal and take out negative pressure to -0.1MPa, dipping 3 is small
When.
The multiphase nitride combined silicon carbide product impregnated is positioned in kiln, is warming up to 900 DEG C, keeps the temperature 6 hours.
Cut from the product after firing 3 sizes be 165 × 114 × 22mm sample, test 3 samples volume and
Quality is then placed in trial furnace.1000 DEG C are warming up to according to ASTM-C863 standards, with 32kg/ (m3.h rate) is passed through water steaming
Vapour keeps the temperature 500 hours.After blowing out cooling, volume and quality after its oxidation of taking-up sample testing calculate volume change and matter
Quantitative change rate.As a result it is：Volume change is respectively+0.84% ,+0.67% ,+0.91%, mass change for+1.90% ,+
1.52%、+2.18%。
Claims (7)
1. a kind of phosphorous nitride combined silicon carbide material, it is characterised in that：The phosphorous nitride combined silicon carbide material
Raw material forms and mass percent is：Metallic silicon power 3 ~ 25%, silicon-carbide particle 60 ~ 70%, carbide fine powder 8 ~ 30%, silicon powder 0
~ 6%, phosphorus additive 0.1 ~ 3%；The phosphorous nitride combined silicon carbide material, using silicon carbide as principal crystalline phase, passes through metallic silicon
The nitridation reaction that silicon nitride and metallic silicon, silicon powder and nitrogen are generated with the nitridation reaction of nitrogen generates silicon oxynitride, so as to
Formed using silicon nitride or silicon oxynitride with silicon nitride as the phosphorous nitride combined silicon carbide material with reference to phase.
2. a kind of phosphorous nitride combined silicon carbide material as described in claim 1, it is characterised in that：The phosphorus additive is
Solid-state or liquid.
3. a kind of phosphorous nitride combined silicon carbide material as described in claim 1, it is characterised in that：The phosphorus additive
For solid-state, as one in sodium tripolyphosphate, calcium phosphate, magnesium phosphate, basic zirconium phosphate, chromium phosphate, aluminium dihydrogen phosphate, composite phosphate
Kind or several mixing.
4. a kind of phosphorous nitride combined silicon carbide material as described in claim 1, it is characterised in that：The phosphorus additive
For liquid, the phosphorus additive is phosphate solution or the phosphoric acid solution of concentration 20%-85%.
5. a kind of phosphorous nitride combined silicon carbide material as claimed in claim 4, it is characterised in that：The phosphate is molten
Liquid is the mixing of one or more of sodium tripolyphosphate solution, sodium hexametaphosphate solution, phosphate dihydrogen aluminum solution.
6. a kind of phosphorous nitride combined silicon carbide material as described in claim 1, it is characterised in that：The phosphorus additive
Addition is 0.3 ~ 1.5%.
7. the preparation method for preparing phosphorous nitride combined silicon carbide material described in claim 1 is：
Solid-state phosphorus additive is mixed with metallic silicon power, silicon-carbide particle, carbide fine powder and silicon powder, through being kneaded, being molded,
Dry, Nitride firing, forms phosphorous nitride combined silicon carbide material；It is as follows：
（1）Carbide fine powder, metallic silicon power, silicon powder and phosphorus additive are blended together into mixing fine powders in advance, then by mixing fine powders and carbon
Silicon carbide particle and the bonding agent mixing in kneading machine, on forming machine compression moulding green compact are made；
（2）By step（1）In the green compact that are pressed into be positioned over 60~180 DEG C and dried stage by stage, total drying time is no less than
24 hours；
（3）Above-mentioned dried green body is placed in high temperature firing under nitrogen atmosphere, heating up process is continuous warming process, most
High firing temperature is 1350~1500 DEG C, and soaking time is 5~15 hours；
（4）Cool to room temperature with the furnace, products obtained therefrom is the phosphorous nitrogen oxide combined silicon carbide material；
Or, the preparation method is：
（1）Carbide fine powder, metallic silicon power, silicon powder are blended together into mixing fine powders in advance, then by mixing fine powders and silicon-carbide particle and
Bonding agent mixing in kneading machine, on forming machine compression moulding green compact are made；
（2）By step（1）In the green compact that are pressed into be positioned over 60~180 DEG C and dried stage by stage, total drying time is no less than
24 hours；
（3）Above-mentioned dried green body is placed in high temperature firing under nitrogen atmosphere, heating up process is continuous warming process, most
High firing temperature is 1350~1500 DEG C, and soaking time is 5~15 hours；
（4）It cools to room temperature with the furnace and obtains nitride combined silicon carbide material；
（5）Obtained nitride combined silicon carbide material is put into the phosphorus additive of liquid, negative pressure impregnation 3-12 hours；
（6）, by after dipping nitride combined silicon carbide material carry out secondary heat treatment, heating up process be continuous warming mistake
Journey, 900 ~ 1100 DEG C of secondary heat treatment maximum temperature, soaking time 6-8 hours.
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